Herbicidal n,n-dialkenyl-3-chlorobenzamides and method



United States Patent 3,436,208 HERBICIDAL N,N-DIALKENYL-3-CHLOR0-BENZAMIDES AND METHOD Alan J. Lemin, Richland Township, KalamazooCounty,

Mich., assignor to The Upjohn Company, Kalamazoo,

Mich a corporation of Delaware No Drawing. Filed Mar. 22, 1961, Ser. No.97,445

Int. Cl. A01n 7/00, 9/20; C07c 103/30 US. Cl. 71118 6 Claims Thisinvention pertains to novel chemical compounds, novel compositions and anovel process. More particularly, the invention relates to novelN-alkylchlorobenzamides, novel herbicidal compositions containing thesame, and a novel process for preventing germination of undesired plantseeds and controlling the pre-emergence growth of such plants.

The economic damage caused by weeds in field crops is well known. Weedsdamage field crops and reduce productivity by competing with the cropplants for mineral nutrients, nitrogen, water, and sunlight. In additionto economic damage to field crops, weeds such as dandelions andcrab-grass frustrate the establishment and maintenance of uniform turfson home lawns, golf courses, and similar areas. Among the methods forcombatting weeds that have been tried, selective chemical inhibitionappears to hold promise of being efiicacious and economical, and a greatmany chemical herbicides have been contrived.

An object of this invention is to provide compositions for preventingthe germination of undesired plant seeds. Another object of theinvention is to provide means for preventing the germination ofundesired plant seeds and for controlling the growth of noxious weeds infield crops and turf. A further object of the invention is to providemeans for controlling noxious weeds such as Johnsongrass, crab-grass,pigweed, quack-grass, Wild oats, foxtails, mustards, purslane,lambsquarters, sheep sorrel, and the like in crops such as cerealgrains, cotton, peanuts, beans, and strawberries, and in turf.

It has now been found in accordance with the invention thatN-alkenylchlorobenzamides represented by the formula 01 Cln wherein R isalkenyl of from 3 to 4 carbon atoms, i.e., allyl, methallyl, 3-butenyl,and crotyl; R is selected from the group consisting of hydrogen andalkenyl (as defined above); and n is an integer from 0 to 2, inclusive,are eifective pre-emergence herbicides useful in preventing germinationof seeds and controlling the pre-emergence growth of plants byinterfusing a soil with a herbicidally effective amount thereof, thuscontacting plant seeds and embryonic plants in order to bring about thedesired herbicidal effects.

The novel N-alkenylchlorobenzamides of this invention can be readilyprepared by methods known in the art for preparing benzamides, forexample, by reacting a chlorobenzoic acid represented by the formulawherein n is as defined above, with thionyl chloride to obtain thecorresponding chlorobenzoyl chloride, and then obtaining the amide byreacting the chlorobenzoyl chlo- 3,436,208 Patented Apr. 1, 1969 ridewith a primary or secondary amine represented by the formula R2 (III)wherein R and R are as defined above.

Chlorobenzoic acids having Formula II above, e.g., 3- chloro-,2,3-dichl0ro-, 3,4-dichloro, 3,5-dichloro, 2,3,4- trichloro-,2,3,5-trichloro, 2,3,6-trichloro-, and 3,4,5-trichlorobenzoic acids areknown compounds and methods for their preparation are recorded in theliterature; for example, see Huntress, Organic Chlorine Compounds, JohnWiley and Sons, Inc., New York, 1948.

The primary and secondary amines having Formula III above, e.g.,allylamine, methallylamine, 3-butenylamine, crotylamine, diallylamine,dimethallylamine (Tamele et al., Ind. Eng. Chem. 33, 1l5l20, 1941),N-methallylcrotylamine (ibid.), di-3-butenylamine (Reppe et al., Ann.596, -158, 1955), and dicrotylamine (Berthold, Chem. Ber. 90, 27432747,1957) are known compounds.

The chlorobenzoyl chloride and the primary or secondary amine arereacted in the presence of a solvent. Suitable solvents include benzene,diethyl ether, dioxane, water, toluene, and the like, or mixturesthereof. Stoichiometrically, the reaction requires one mole of amine foreach mole of acid halide. However, the reaction releases one mole ofhydrogen chloride; so an excess of amine, preferably at least one moleexcess, should be provided. In lieu of an excess of the amine, anothersuitable acid acceptor, for example, triethylamine, pyridine, picoline,sodium hydroxide, and the like can be utilized. The reaction can becarried out at temperatures in the range of about 0 C. to about C. or upto the reflux temperature of the solvent. The N-alkenylchlorobenzamideproduct is recovered by conventional methods, for example, filtering,washing to remove amine salts, and recrystallization.

Illustrative N-alkenylchlorobenzamides prepared as disclosed aboveinclude N-allyl-3-chlorobenzamide, N-rnethallyl 3 chlorobenzamide,N-(3-butenyl)-3-chlorobenzamide, N-crotyl-3-chlorobenzamide,N,N-diallyl-3-chlorobenzamide, N,N-di(B-butenyl) 3 chlorobenzamide, N-methally'l-N-crotyl-3-chlorobenzamide, N,N-dimethallyl-3-chlorobenzamide, N,N-dicrotyl-3-chlorobenzamide, N,N-diallyl-2,3-dichlorobenzamide, N-methyallyl-N-crotyl-Z,3-dichlorobenzamide, N,N-dicr0tyl-3,4-dichlorobenzamide,N,N-di(3-butenyl)-3,4-dichlorobenzamide, N,N-diallyl-3,4-dichlorobenzamide, N-allyl-3,S-dichlorobenzamide, N-methallyl-N-crotyl-3,S-dichlorobenzamide, N,N-diallyl-3,S-dichlorobenzamide, N,N diallyl 2,3,4 trichlorobenzamide, N,N di( 3butenyl)-2,3,4-trichlorobenzamide, N- allyl-2,3,5,trichlorobenzamide,N-methallyl-2,3,5-trichlorobenzamide,N,N-diallyl-2,3,S-trichlorobenzamide, N,N-dimethallyl-2,3,S-trichlorobenzamide, N-(3-butenyl) 2,3,6-trichlorobenzamide, N,N diallyl 2,3,6 trichlorobenzamide, N (3butenyl) 3,4,5 trichlorobenzamide, N- allyl-3,4,5-trichlorobenzamide,and N,N-diallyl-3,4,5-trichlorobenzamide.

Any N-alkenylchlorobenzamide as set forth above can be effectivelyemployed as active ingredient in the herbicidal compositions and processof this invention, the 3- chloro, 3,4-dichloro-, 2,3,5-trichloro-, and2,3,6-trichlorobenzamides of Formula I being preferred. It is alsopreferred that the N-alkenylchlorobenzamides of this invention beN,N-dialkenyl-substituted on the amido nitrogen.

Some of the N-alkenylchlorobenzamides are solids at ordinarytemperatures and some are liquids. It should be understood, therefore,that the proportion of a liquid active ingredient in the granular, dust,and dispersible powder formulations of this invention be consistent withobtaining a dry, free-flowing composition. Pastes, of course, can beprepared as well.

The herbicidal compositions according to the invention includesolutions, emulsions, suspensions, dispersible powders, emulsifiableconcentrates, granular formulations, pastes, and dusts. All of thesecompositions comprise an N-alkenylchlorobenzamide in accordance withFormula I in dispersed or readily dispersible form and a carrier, withor without adjuvants. In general, selective inhibition of undesired Weedspecies in the presence of field corps or in turf is obtained byemploying a phytonomic carrier, that is to say, a carrier which can beapplied to plants without phytotoxicity or other adverse effects. On theother hand, when general herbicidal activity is desired a phytotoxiccarrier, for example, high-boiling mineral oil fractions orchlorohydrocarbons can be used.

The efiicacy of N-alkenylchlorobenzarnides as preemergence herbicides isof high order, and the compounds can be applied at relatively low ratesper acre for preventing the germination of seeds and controlling thegrowth of plants. For example, N,N-diallyl-3-chloro-,3,4- dichloro-,2,3,5-trichloro-, and 2,3,6-trichlorobenzamides gave complete orsubstantially complete inhibition of crabgrass, foxtails, andJohnson-grass, when applied at the rate of 5 to 20 lbs. per acre tonewly seeded plots. Little or no phytotoxic effect is apparent amongfield crop plants such as corn, Wheat, rye, soybeans, and peanuts atthese and even somewhat higher rates of application. At high rates ofapplication, e.g., 30 lbs. per acre or more, the compounds arephytotoxic to corn, wheat, and rye; but legumes, such as peanuts, arenot killed. Illustratively, excellent control of crab-grass in lawns hasbeen obtained using concentrations of N,N-diallyl-3-chlorobenzamideranging from 700 ppm. (parts per million) to 12,000 ppm. applied at therate of 2.5 to lbs. per acre without damage to the turf. In general, adesired rate of application can be achieved by distributing, over thearea to be treated, an aqueous composition in accordance with theinvention, containing from about 700 ppm. to about 30,000 p.p.m. ofactive ingredient. It will be understood, of course, that a choice ofconcentration of active ingredient depends upon the method ofapplication as well as the type of composition and the degree ofherbicidal control desired. In general, concentration is not criticalwithin the range indicated since an effective quantity of activeingredient can be applied to a given area by applying greater quantitiesof a low concentration than of a higher concentration. The concentrationof active ingredient in the dispersible powder and emulsifiableconcentrates from which the aqueous compositions are prepared can be ashigh as 99.5% by weight. The concentration of active ingredient in thedust and granular formulations of the invention can vary from about0.25% to about 80% or more, but advantageously is of the order of 0.50%to by weight. The choice of active-ingredient concentration in solidformulations will in some instances be influenced by the physicalproperties of the active ingredient, as has been noted above and will bewell understood by persons skilled in the formulation art.

The granular formulations of this invention are prepared With about0.25% to about 80%, preferably 0.50% to 20% by weight, of activeingredient and a granular carrier, for example, vermiculite,pyrophyllite, an attapulgite. The active ingredient can be dissolved ina volatile solvent such as ethylene dichloride, methylene chloride,acetone, and the like, and sprayed on the granular carrier as it ismixed and tumbled. The granules are then dried. The granular carrier canrange in particle size from about 10 to about 60 mesh, preferably aboutto 60 mesh.

The herbicidal dust compositions of the invention are prepared byintimate admixture f from about 0.25% to about 80% by weight, preferably0.50% to 20% of the active ingredient, with a solid pulverulent carrierwhich maintains the composition in a dry, free-flowing state. In thecase of the N-alkenylchlorobenzamides that are solids at ordinarytemperatures, the herbicidal dusts of the invention can be prepared byadmixing with a solid diluent and then milling. Preferably, however, theactive ingredient is dissolved in a volatile organic solvent, of thekinds indicated above, and then sprayed on the solid carrier so as toassure thorough distribution. The mixture is then dried and milled tothe desired size, e.g., less than about 60 microns.

Solid carriers that can be used in the dust compositions of theinvention include the natural clays such as China clay and bentonite,minerals in the natural state such as talc, pyrophyllite, quartz,diatomaceous earth, Fullers earth, chalk, and rock phosphate, and thechemically modified minerals such as Washed bentonite, precipitatedcalcium phosphate, precipitated calcium carbonate, precipitated calciumsilicate, and collodial silica. The solid diluents which can be employedin the composition also include solid, compounded fertilizers. Suchsolid compositions can be applied to soil in the form of dusts by theuse of conventinal machinery.

Dispersible powders are prepared by incorporating a surfactant in a dustcomposition prepared as described above. Such a dispersible powder canbe dispersed in water to any desired concentration and applied to soilby conventional spray equipment. Conveniently, the dispersible powdersare formulated with concentrations of active ingredient up to aboutpreferably about 10% to 60% by weight. Surfactants useful in preparingsuch dispersible powder compositions include alkyl sulfates andsulfonates, alkyl aryl sulfonates, sulfosuccinate esters,polyoxyethylene sulfates, polyoxyethylene-sorbitan monolaurate, alkylaryl polyether sulfates, alkyl aryl polyether alcohols, alkylnaphthalene sulfonates, alkyl quaternary ammonium salts, sulfated fattyacids and esters, sulfated fatty acid amides, glycerol mannitan laurate,polyalkylether condensates of fatty acids, lignin sulfonates, and thelike. A preferred class of surfactants includes blends of sulfonatedoils and polyalcohol carboxylic acid esters (Emcol H-77), blends ofpolyoxyethylene ethers and oilsoluble sulfonates (Emcol H-400), blendsof alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (TritonsX-l51, X-l6l, and Xl7l), e.g., about equal parts of sodium kerylbenzenesulfonate and isooctylphenoxy polyethoxy ethanol containing about 12ethoxy groups, and blends of calcium alkyl aryl sulfonates andpolyethoxylated vegetable oils (Agrimul N 8). It will be understood, ofcourse, that the sulfate and sulfonate surfactants suggested above willpreferably be used in the form of their soluble salts, for example,their sodium salts. All of these surfactants are capable of reducing thesurface tension of water to less than about 40 dynes per centimeter inconcentrations of about 1% or less. The dispersible powder compositionscan be formulated with a mixture of surfactants of the types indicatedif desired.

A suitable dispersible powder formulation is obtained by blending andmilling 327 lbs. of Georgia clay, 4.5 lbs. of isooctylphenoxy polyethoxyethanol (Triton Xl00) as a wetting agent, 9 lbs. of a polymerized sodiumsalt of substituted benzoid long-chain sulfonic acid (Band 27) as adispersing agent, and 113 lbs. of the active ingredient. The resultingformulation has the following percentage composition (parts herein areby weight unless otherwise specified):

Percent Active ingredient 25 Isooctylphenoxy polyethoxy ethanol 1Polymerized sodium salt of substituted benzoid long-chain sulfonic acid2 Georgia clay 72 This formulation, when dispersed in water at the rateof 10 lbs. per gals, gives a spray formulation containing about 0.3%(3000 ppm.) active ingredient which can be applied to soil or turf atthe rate of 40' gals. per acre to give a total application of activeingredient of 1 lb. per acre.

The compounds of this invention can be applied to soil and turf inaqueous sprays without a solid carrier. However, since the compoundsthemselves are relatively insoluble in water they are preferablydissolved in a suitable inert organic solvent carrier. Advantageously,the solvent carrier is immiscible with water so that an emulsion of thesolvent carrier in water can be prepared. If, for example, awater-miscible solvent carrier such as ethanol is used the solventcarrier will dissolve in water and any excess N-alkenylchlorobenzamidewill be thrown out of solution. (The compounds dissolve in water toabout 50 ppm.) In an emulsion, the solvent phase is dispersed in thewater phase and the active ingredient is held in solution in thedispersed phase. In this way, uniform distribution of active ingredientin an aqueous spray is achieved. A solvent carrier in whichN-alkenylchlorobenzamides are highly soluble is desirable so thatrelatively high concentrations of active ingredient can be obtained.Sometimes, one or more solvent carriers with or -without cosolvents canbe used in order to obtain concentrated solutions of the activeingredient, the main consideration being to employ a water-immisciblesolvent for the N- alkenylchlorobenzamide that will hold the compound insolution over the range of concentrations useful for preventinggermination of undesired seeds and controlling growth of plants.

The emulsifiable concentrates of the invention are prepared bydissolving the active ingredient and a surfactant in a substantiallywater-immiscible solvent carrier (i.e., a solvent carrier which issoluble in water to the extent of less than 2.5% by volume attemperatures of the order of to C.), for example, cyclohexanone, methylpropyl ketone, summer oils, ethylene dichloride, aromatic hydrocarbonssuch as benzene, toluene, and xylene, and high-boiling petroleumhydrocarbons such as kerosene, diesel oil, and the like. If desired, acosolvent such as methyl ethyl ketone, acetone, isopropanol and the likecan be included with the solvent carrier in order to enhance thesolubility of the active ingredient. Aqueous emulsions are then preparedby mixing with water to give any desired concentration of activeingredient. The surfactants which can be employed in the aqueousemulsions of the invention are those types noted above. Mixtures ofsurfactants can be employed if desired.

Advantageously, the concentration of active ingredient in theemulsifiable concentrates can range from about 5% to about 50% byweight, preferably from about 10% to A concentrate comprising 20% (byweight) of active ingredient dissolved in a water-immiscible solvent ofthe kind noted above can be admixed with an aqueous medium in theproportions of about 13 ml. of concentrate with 1 gal. of medium to givea mixture containing about 700 parts of active ingredient per millionparts of liquid carrier. Similarly, 1 qt. of a 20% concentrate mixedwith 40 gals. of water provides about 1200 p.p.m. of active ingredient.In the same manner, more concentrated solutions of active ingredient canbe prepared.

The concentrate compositions of the invention which are intended for usein the form of aqueous dispersions or emulsions can also comprise ahumectant, that is to say, an agent which will delay the drying of thecomposition in contact with material to which it has been applied.Suitable humectants include glycerol, diethylene glycol, solubilizedlignins, such as calcium lignosulfonate, and the like.

The rates of application to soils or turf to be protected from noxiousweeds will depend upon the species of plants to be controlled, thepresence or absence of desirable species, the season of year at whichtreatment is undertaken, and the method and efficiency of application.In general, selective herbicidal activity is obtained when the activeingredients are applied at the rate of about 0.125 to about lbs. peracre, preferably at the rate of 0.25 to 25 lbs. per acre.

The compositions containing N-alkenylchlorobenzamides, according to theinvention, can be interfused with soil by conventional methods. Forexample, an area of soil can be treated prior to or after seeding byspreading a granular formulation in accordance with the invention on theplant growth medium with or without mixing. For home application, aconventional hand propelled spreader is satisfactory. Dispersible powdersuspensions, emulsions, or solutions can be sprayed from boom-type powersprayers or from hand-operated knapsack sprayers. Dusts can be appliedby power clusters, or by hand-operated dusters. Dusts and granularformulations can also be applied at the time of seeding in bandsspanning the seeded rows.

The term soil is employed in the present specification and claims in itsbroadest sense. Hence the term soil refers to a material in which plantscan take root and grow, and includes not only earth but compost, manure,muck, humus, sand, and the like.

The following examples are illustrative of the process and products ofthe present invention, but are not to be construed as limiting.

Example 1.Preparation of N,N-diallyl-3- chlorobenzamide (A)3-chlorobenzoyl ch1oride.A mixture consisting of 31.3 g. (0.2 mole) of3-chlo-robenzoic acid, 30ml. of thionyl chloride, and 30 ml. of benzenewas heated at reflux temperature for 30 min. and was then evaporated todryness under reduced pressure. Benzene (30 ml.) was added to theresidue and the mixture was again evaporated to dryness under reducedpressure. The residue, 3-chlorobenzoyl chloride, was an oil.

(B) N,N-diallyl-3-chlorobenzamide.The 3-chlorobenzoyl chloride obtainedin Part A was added to a stirred solution of 45 ml. of diallylamine in30 ml. of diethyl ether. The temperature of the reaction mixture wasmaintained at about 25 C. for 10 min., after which 300 ml. of water wasadded. The mixture was shaken and the phases were separated, the aqueousphase being discarded. The organic phase was washed with water and driedwith anhydrous sodium sulfate. The sodium sulfate was removed byfiltration, the filtrate was evaporated to dryness, and the residue wasdistilled under reduced pressure. There was thus obtained 35.4 g. (75.2%yield) of N,N-diallyl-3-chlorobenzamide as an oil having a boiling pointof C. at a pressure of 0.3 mm. of mercury; 11 15468.

Analysis-Calculated for C H CINO: C, 66.24; H, 5.99; Cl, 15.04; N, 5.94.Found: C, 66.18; H, 6.09; Cl, 15.01; N, 6.12.

Following the same procedure but substituting allylamine,methallylamine, 3-butenylamine, crotylamine, dimethallylamine,N-methallylcrotylamine, di-3-butenylamine, and dicrotylamine fordiallylarnine, there were obtained N-allyl-3-chlorobenzamide,N-methallyl-3-chlorobenzamide, N-(3-butenyl)-3-chlorobenzamide,N-crotyl-3-chlorobenzamide, N,N-dimethallyl-3-chlorobenzamide,N-methallyl-N-3-crotyl-3-chlorobenzamide,N,N-di(3-butenyl)-3-chlorobenzamide, and N,N-dicrotyl-3-chlorobenzamide,respectively.

Example 2.Preparation of N,N-diallyl-2,3- dichlorobenzamide Followingthe procedure of Example I, Part B, but substituting 2,3-dichlorobenzoylchloride for 3-chlorobenzoyl chloride, there was obtainedN,N-diallyl-2,3-dichlorobenzamide.

Example 5.Preparation of N,N-diallyl-2,3,4- trichlorobenzamide Followingthe procedure of Example 1, Part B, but substituting2,34-trichlorobenzoyl chloride for 3-chlorobenzoyl chloride, there wasobtained N,N-diallyl-2,3,4- trichlorobenzamide.

Example 6.Preparation of N,N-diallyl-2,3,5-

trichlorobenzamide Following the procedure of Example 1, Part B, butsubstituting 2,3,5-trichlorobenzoyl chloride for 3-chlorobenzoylchloride, there was obtained N,N-diallyl-2,3,5- trichlorobenzamide.

Example 7.Preparation of N,N-diallyl-2,3,6- trichlorobenzamide Followingthe procedure of Example 1, Part B, but substituting2,3,6-trichlorobenzoyl chloride for 3-chlorobenzoyl chloride, there wasobtained N,.N-diallyl-2,3,6- trichlorobenzamide.

Example 8.-Preparation of N,N-diallyl-3,4,5- trichlorobenzamideFollowing the procedure of Example 1, Part B, but substituting3,4,5-trichlorobenzoyl chloride for 3-chloro benzoyl chloride, there wasobtained N,N-diallyl-3,4,5- trichlorobenzamide.

Example 9 A granular formulation having the following percentagecomposition:

Percent N,N-diallyl-3-chlorobenzamide 3.7 vermiculite (30/60 mesh) 96.3i

was prepared by spraying a solution of 220 g. ofN,N-diallyl-3-chlorobenzamide in 1000 ml. of methylene chloride on 5780g. of vermiculite (30 to 60 mesh) while the vermiculite was beingtumbled and stirred so as to assure even distribution. The methylenechloride was then evaporated, leaving the N,N-diallyl-3-chlorobenzamideadsorbed on the vermiculite.

The herbicidal efficacy of the formulation was then determined byspreading the treated vermiculite on test plots of soil planted to rowsof crab-grass, green foxtail, Johnson-grass, quack-grass, wheat, rye,peanuts, and corn. After 21 days the inhibition of seed germination andplant growth was noted, when compared with control plots of the samecultural treatment. The results are shown in the following table.

8 In the same manner granular compositions containingN,N-diallyl-3,4-dichloro-, 2,3,5-trichloro-, and2,3,6-trichlorobenzamide were prepared and tested, with similar results.

Example 10 A dispersible powder concentrate having the followingpercentage composition:

Percent N,N-dially1-2,3,S-trichlorobenzamide 45.8 Polymerized sodiumsalt of substituted benzoid longchain sulfonic acid (Daxad 27) 9.2Kaolinite 45.0

was prepared by mixing 250 g. of N,N-diallyl-2,3,5-trichlorobenzamide,g. of polymerized sodium salt of substituted benzoid long-chain sulfonicacid (Daxad 27), and 245 g. of kaolinite. The mixture was milled to aparticle size averaging 5 to 30 microns. It was suspended in 10 gals. ofwater, giving an aqueous spray containing about 6500 p.p.m. of activeingredient.

Example 11 An emulsifiable concentrate having the following percentagecomposition:

Percent N,N-diallyl-2,3,6-trichlorobenzamide 15.0 Technical alkylnaphthalene boiling at 238 to 293 C. (Velsicol AR50) 19.7

Xylene 17.4

Isopropanol 17.4

Ethylene dichloride 25.4

Blend of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols(Triton X151) 5.1

was prepared by mixing 15.0 lbs. of N,N-diallyl-2,3,6trichlorobenzamide, 19.7 lbs. of the technical alkyl naphthalene(Velsicol AR50), 17.4 lbs. of xylene, 17.4 lbs. of isopropanol, 25.4lbs. of ethylene dichloride, and 5.1 lbs. of the blend of alkyl arylsulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151).

6.67 lbs. of the concentrate mixed with 10 gals. of water gave a sprayemulsion containing 12,000 p.p.m. ofN,N-diallyl-2,3,6-trichlorobenzamide.

Example 12 An emulsifiable concentrate having the following percentagecomposition:

Percent N,N-diallyl-2,3,S-trichlorobenzamide 40.0 Technical alkylnaphthalene boiling at 238 to 293 C. (Velsicol ARSO) 13.7

Xylene 12.3

Isopropanol 11.3

Ethylene dichloride 17.7

Blend of alkyl aryl sultonates and alkylphenoxy polyethoxy ethanols(Triton X-151) 5.0

was prepared by mixing 40.0 lbs. ofN,N-diallyl-2,3,5-trichlorobenzamide, 13.7 lbs. of the technical alkylnaphthalene (Velsicol AR50), 12.3 lbs. of xylene, 11.3 lbs. ofisopropanol, 17.7 lbs. of ethylene dichloride, and 5.0 lbs. of the blendof alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (TritonX-151).

1.67 lbs. of the concentrate mixed with 10 gals. of water gave a sprayemulsion containing 8,000 ppm. of N,N-diallyl-2,3 ,5-trich'lorobenzamide.

TABLE Rates of Percent inhibition application, active ingre- GreenQuack- Johnsondient in Corn Wheat Rye Peanuts Grabgrass Foxtail grassgrass lbs/acre 20 0 I) 0 100 100 100 100 10 0 0 0 0 100 100 100 100 0 Ul) 100 50 9 Example 13 A dispersible powder concentrate having thefollowing precentage composition:

Percent N,N-diallyl-2,3,6-trichlorobenzamide 50 Kaolinite clay (finelydivided) 46 Sodium salt of condensed mononaphthalene sulfonic acid(Lomar D) 4 Was prepared by mixing 50 g. ofN,N-diallyl-2,3,6-trichlorobenzamide, 46 g. of the kaolinite clay, and 4g. of a sodium salt of condensed mononaphthalene sulfonic acid (LomarD). The mixture was milled to an average particle size of to 30 microns.

Example 14 A granular formulation having the following percentagecomposition:

Percent N,N-diallyl-2,3,5-trich1orobenzamide 1 Pyrophyllite (30/60 mesh)99 was prepared by dissolving 1.0 lb. of N,N-diallyl-2,3,5-trichlorobenzamide in 10.0 1. of ethylene dichloride and spraying thesolution on 99.0 lbs. of pyrophyllite. The granules were dried and thenpackaged for use.

Example 15 A dust formulation having the following percentagecomposition:

Percent N,N-diallyl-3-chlorobenzamide 5.0 Vermiculite (30/60 mesh) 95.0

then pulverized to a particle size averaging 5 to 30 microns.

I claim:

1. N,N-dialkenyl-3-chlorobenzamide wherein alkenyl is of from 3 to 4carbon atoms, inclusive.

2. N,N-diallyl-3-chlorobenzamide.

3. Herbicidal composition of matter comprising a herbicidally effectiveamount of N,N-dialkenyl-3-chlorobenzamide and a dispersible carriertherefor wherein alkenyl is of from 3 to 4 carbon atoms, inclusive.

4. Emulsifiable concentrate comprising, as the essential activeingredient, N,N-dialkenyl-3-chlorobenzamide wherein alkenyl is of from 3to 4 carbon atoms, inclusive.

5. Herbicidal composition comprising from about 0.25% to about ofN,N-dialkenyl-3-chlorobenzamide wherein alkenyl is of from 3 to 4 carbonatoms, inclusive, and a solid particulate carrier therefor.

6. The method of preventing germination of plant seeds and controllingpre-emergence growth of plants which comprises interfusing soil with aherbicidally effective amount of N,'N-dialkenyl 3 chlorobenzamidewherein alkenyl is of from 3 to 4 carbon atoms, inclusive, and a solidparticulate carrier therefor.

References Cited UNITED STATES PATENTS 3,077,498 2/1963 Baker et a1.712.6 XR 3,014,965 12/1961 Newcomer et al. 712.6 XR 2,412,510 12/1946-Jones 712.6 2,551,891 5/1951 Martin 167-30 XR FOREIGN PATENTS 785,98911/1957 Great Britain.

OTHER REFERENCES Pizey et 211.: Jr. Science Food Agri, vol. 10, November1959, pages 577584.

JAMES O. THOMAS, 111., Primary Examiner.

US. Cl. X.R.

1. N,N-DIALKENYL-3-CHLOROBENZAMIDE WEREHIN ALKENYL IS OF FROM 3 TO 4CARBON ATOMS, INCLUSIVE.
 6. THE METHOD OF PREVENTING GERMINATION OFPLANT SEEDS AND CONTROLLING PRE-EMERGENCE GROWTH OF PLANTS WHICHCOMPRISES INTERFUSING SOIL WITH A HERBICIDALLY EFFECTIVE AMOUNT OFN,N-DIALKYNYL - 3 - CHLOROBENZAMIDE WHEREIN ALKENYL IS OF FROM 3 TO 4CARBON ATOMS, INCLUSIVE, AND A SOLID PARTICULATE CARIER THEREFOR.